Active substance combinations having insecticidal and acaricidal properties

ABSTRACT

The invention relates to novel active compound combinations of certain cyclic ketoenols and certain active compounds that together have unexpectedly good insecticidal and acaricidal properties.

This application is a divisional of U.S. application Ser. No.10/842,396, filed May 10, 2004, now U.S. Pat. No. 7,098,225, issued Aug.29, 2006, which is a divisional of U.S. application Ser. No. 10/257,043,filed Oct. 7, 2002, now U.S. Pat. No. 6,762,183, issued Jul. 13, 2004,which was filed under 35 U.S.C. 371 as a national stage application ofInternational Application No. PCT/EP01/03602, filed Mar. 29, 2001, whichwas published in German as International Patent Publication WO 01/76369on Oct. 18, 2001 , which is entitled to the right of priority of GermanPatent Application 100 17 881.2, filed Apr. 11, 2000.

The present invention relates to novel active compound combinationscomprising known cyclic ketoenols on the one hand and other knowninsecticidally active compounds on the other hand and which are highlysuitable for controlling animal pests such as insects and undesiredacarids.

It is already known that certain cyclic ketoenols have insecticidal andacaricidal properties (EP-A-528 156). WO 95/01971, EP-A-647 637, WO96/16061, WO 96/20196, WO 96/25395, WO 96/35664, WO 97/02243, WO97/01535, WO 97/36868, WO 97/43275, WO 98/05638, WO 98/06721, WO99/16748, WO 99/43649, WO 99/48869 and WO 99/55673 describe furtherketoenols having insecticidal and acaricidal properties. The activity ofthese substances is good; however, at low application rates it issometimes unsatisfactory.

Furthermore, it is already known that numerous heterocycles, organotincompounds, benzoylureas and pyrethroids have insecticidal and acaricidalproperties (cf. WO 93-22 297, WO 93-10 083, DE-A 2 641 343, EP-A-347488, EP-A-210 487, U.S. Pat. No. 3,264,177 and EP-A-234 045). However,the activity of these substances is not always satisfactory.

It has now been found that compounds of the formula (I)

in which

-   X represents C₁-C₆alkyl, halogen, C₁-C₆alkoxy or    C₁-C₃-halogenoalkyl,-   Y represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or    C₁-C₃-halogeno-alkyl,-   Z represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,-   n represents a number from 0 to 3,-   A represents hydrogen or in each case optionally halogen-substituted    straight-chain or branched C₁-C₁₂-alkyl, C₃-C₈-alkenyl,    C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl,    C₁-C₈-polyalkoxy-C₂-C₈-alkyl, C₁-C₁₀-alkylthio-C₂-C₈-alkyl or    cycloalkyl having 3-8 ring atoms which may be interrupted by oxygen    and/or sulphur and represents in each case optionally halogen-,    C₁-C₆-alkyl-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-,    C₁-C₆-halogenoalkoxy- or nitro-substituted phenyl or    phenyl-C₁-C₆-alkyl,-   B represents hydrogen, C₁-C₆-alkyl or C₁-C₆-alkoxy-C₂-C₄-alkyl    or in which-   A and B together with the carbon atom to which they are attached    form a saturated or unsaturated 3- to 8-membered ring which is    optionally interrupted by oxygen and/or sulphur and optionally    substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,    C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio or    optionally substituted phenyl or is optionally benzo-fused,-   G represents hydrogen (a) or represents a group

-   -   in which

-   R¹ represents in each case optionally halogen-substituted    C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl,    C₁-C₈-alkylthio-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl or    cycloalkyl having 3-8 ring atoms which may be interrupted by oxygen    and/or sulphur atoms,    -   represents optionally halogen-, nitro-, C₁-C₆-alkyl-,        C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or        C₁-C₆-halogenoalkoxy-substituted phenyl,    -   represents optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,        C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substituted        phenyl-C₁-C₆-alkyl,    -   represents in each case optionally halogen- and/or        C₁-C₆-alkyl-substituted pyridyl, pyrimidyl, thiazolyl or        pyrazolyl,    -   represents optionally halogen- and/or C₁-C₆-alkyl-substituted        phenoxy-C₁-C₆-alkyl,

-   R² represents in each case optionally halogen-substituted    C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl or    C₁-C₈-polyalkoxy-C₂-C₈-alkyl,    -   represents in each case optionally halogen-, nitro-,        C₁-C₆-alkyl-, C₁-C₆-alkoxy- or C₁-C₆-halogenoalkyl-substituted        phenyl or benzyl,

-   R³ represents optionally halogen-substituted C₁-C₈-alkyl, represents    in each case optionally C₁-C₄-alkyl-, halogen-,    C₁-C₄-halogenoalkyl-, C₁-C₄-alkoxy-, C₁-C₄-halogenoalkoxy-, nitro-    or cyano-substituted phenyl or benzyl,

-   R⁴ and R⁵ independently of one another represent in each case    optionally halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy,    C₁-C₈-alkylamino, di-(C₁-C₈)-alkyl-amino, C₁-C₈-alkylthio,    C₂-C₅-alkenylthio, C₂-C₅-alkinylthio or C₃-C₇-cycloalkylthio,    represent in each case optionally halogen-, nitro-, cyano-,    C₁-C₄-alkoxy-, C₁-C₄-halogenoalkoxy-, C₁-C₄-alkylthio-,    C₁-C₄-halogeno-alkylthio-, C₁-C₄-alkyl- or    C₁-C₄-halogenoalkyl-substituted phenyl, phenoxy or phenylthio,

-   R⁶ and R⁷ independently of one another represent in each case    optionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy,    C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₁-C₈-alkyl, represent optionally    halogen-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkyl- or    C₁-C₆-alkoxy-substituted phenyl, represent optionally halogen-,    C₁-C₆-alkyl-, C₁-C₆-halogenoalkyl- or C₁-C₆-alkoxy-substituted    benzyl or together represent a 5- or 6-membered ring which is    optionally interrupted by oxygen or sulphur and which may optionally    be substituted by C₁-C₆-alkyl,    and

-   1. amitraz

-   -   known from DE-A-2 061 132    -   and/or

-   2. buprofezin

-   -   known from DE-A-2 824 126    -   and/or

-   3. triazamate

-   -   known from EP-A-213 718    -   and/or

-   4. pymetrozin

-   -   known from EP-A-314 615

-   5. pyriproxyfen

-   -   known from EP-A-128 648

-   6. IK 220

-   -   known from BCPC Conf.-Pests Dis. (2000), (Vol. 1), 59 to 65        have very good insecticidal and acaricidal properties.

Surprisingly, the insecticidal and acaricidal action of the activecompound combinations according to the invention considerably exceedsthe total of the actions of the individual active compounds. A truesynergistic effect which could not have been predicted exists, not justa complementation of action.

The active compound combinations according to the invention comprise, inaddition to at least one active compound of the formula (I), at leastone active compound of compounds 1 to 6.

Preference is given to active compound combinations comprising compoundsof the formula (I)

in which

-   X represents C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or    C₁-C₂-halogenoalkyl,-   Y represents hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy or    C₁-C₂-halogeno-alkyl,-   Z represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy,-   n represents 0 or 1,-   A and B together with the carbon atom to which they are attached    form a saturated, optionally C₁-C₄-alkyl- or    C₁-C₄-alkoxy-substituted 5- or 6-membered ring,-   G represents hydrogen (a) or represents the groups

-   -   in which

-   R¹ represents in each case optionally halogen-substituted    C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or cycloalkyl    having 3-7 ring atoms which may be interrupted by 1 or 2 oxygen    and/or sulphur atoms,    -   represents optionally halogen-, nitro-, C₁-C₄-alkyl-,        C₁-C₄-alkoxy-, C₁-C₃-halogenoalkyl- or        C₁-C₃-halogenoalkoxy-substituted phenyl,

-   R² represents in each case optionally halogen-substituted    C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl or C₁-C₆-alkoxy-C₂-C₆-alkyl,    -   represents in each case optionally halogen-, nitro-,        C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₄-halogenoalkyl-substituted        phenyl or benzyl,    -   and at least one active compound of compounds 1 to 6.

Particular preference is given to active compound combinationscomprising the dihydrofuranone derivative of the formula (I-b-1)

and at least one active compound of compounds 1 to 6.

In addition, the active compound combinations may also comprise otherfungicidally, acaricidally or insecticidally active components which maybe admixed.

If the active compounds are present in the active compound combinationsaccording to the invention in certain weight ratios, the synergisticeffect is particularly pronounced. However, the weight ratios of theactive compounds in the active compound combinations may be variedwithin a relatively wide range. In general, the combinations accordingto the invention comprise active compounds of the formula (I) and theco-components in the preferred and particularly preferred mixing ratiosindicated in the table below:

-   -   the mixing ratios are based on weight ratios. The ratio is to be        understood as meaning active compound of the formula (I):        co-component

Particularly preferred Co-component Preferred mixing ratio mixing ratioamitraz  5:1 to 1:20  1:1 to 1:10 buprofezin 10:1 to 1:10 5:1 to 1:5pymetrozin 10:1 to 1:10 5:1 to 1:5 pyriproxyphen 10:1 to 1:10 5:1 to 1:5triazamate 10:1 to 1:10 5:1 to 1:5 IKI 220 10:1 to 1:10 5:1 to 1:5

The active compound combinations according to the invention are suitablefor controlling animal pests, preferably arthropods and nematodes, inparticular insects and arachnids found in agriculture, in animal health,in forests, in the protection of stored products and materials and inthe hygiene sector. They are active against normally sensitive andresistant species, and against all or individual developmental stages.The abovementioned pests include:

-   From the order of the Isopoda, for example, Oniscus asellus,    Armadillidium vulgare, Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus.-   From the order of the Chilopoda, for example, Geophilus carpophagus,    Scutigera spp.-   From the order of the Symphyla, for example, Scutigerella    immaculata.-   From the order of the Thysanura, for example, Lepisma saccharina.-   From the order of the Collembola, for example, Onychiurus armatus.-   From the order of the Orthoptera, for example, Acheta domesticus,    Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus    spp., Schistocerca gregaria.-   From the order of the Blattaria, for example, Blatta orientalis,    Periplaneta americana, Leucophaea maderae, Blattella germanica.-   From the order of the Dernaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Reticulitermes spp.-   From the order of the Phthiraptera, for example, Pediculus humanus    corporis, Haematopinus spp., Linognathus spp., Trichodectes spp.,    Damalinia spp.-   From the order of the Thysanoptera, for example, Hercinothrips    femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.-   From the order of the Heteroptera, for example, Eurygaster spp.,    Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius    prolixus, Triatoma spp.-   From the order of the Homoptera, for example, Aleurodes brassicae,    Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,    Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,    Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,    Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli,    Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix    cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,    Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,    Pseudococcus spp., Psylla spp.-   From the order of the Lepidoptera, for example, Pectinophora    gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis    blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma    neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix    thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,    Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae,    Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa    pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia    kuehniella, Galleria mellonella, Tineola bisselliella, Tinea    pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua    reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona    magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.-   From the order of the Coleoptera, for example, Anobium punctatum,    Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,    Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata,    Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,    Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis,    Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,    Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,    Dernestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp.,    Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus,    Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,    Conoderus spp., Melolontha melolontha, Amphimallon solstitialis,    Costelytra zealandica, Lissorhoptrus oryzophilus.-   From the order of the Hymenoptera, for example, Diprion spp.,    Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.-   From the order of the Diptera, for example, Aedes spp., Anopheles    spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,    Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra    spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus    spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,    Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis    capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza    spp.-   From the order of the Siphonaptera, for example, Xenopsylla cheopis,    Ceratophyllus spp.-   From the class of the Arachnida, for example, Scorpio maurus,    Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,    Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,    Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,    Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,    Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus    spp., Hemitarsonemus spp., Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The active compound combinations can be converted into the customaryformulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethyl-formamide and dimethylsulphoxide, or else water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic materials such as highly-disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, or else synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam formers are: for example nonionic and anionic emulsifierssuch as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates, or else protein hydrolysates; suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchalizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms.

Mixtures with other known active compounds such as herbicides or withfertilizers and growth regulators are also possible.

When used as insecticides, the active compound combinations according tothe invention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergists. Synergists are compounds which increase theaction of the active compounds, without it being necessary for thesynergist added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and stored-product pests, the activecompound combinations are distinguished by an excellent residual actionon wood and clay as well as good stability to alkali on limedsubstrates.

The active compound combinations according to the invention are not onlyactive against plant pests, hygiene pests and stored-product pests, butalso, in the veterinary medicine sector, against animal parasites(ectoparasites) such as hard ticks, soft ticks, mange mites, harvestmites, flies (stinging and licking), parasitizing fly larvae, lice, hairlice, bird lice and fleas. These parasites include:

-   From the order of the Anoplurida, for example, Haematopinus spp.,    Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.-   From the order of the Mallophagida and the suborders Amblycerina and    Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton    spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina    spp., Trichodectes spp., Felicola spp.-   From the order Diptera and the suborders Nematocerina and    Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,    Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,    Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,    Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca    spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp.,    Fannia spp., Glossina spp., Calliphora spp., Lucilia spp.,    Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,    Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.,    Melophagus spp.-   From the order of the Siphonapterida, for example, Pulex spp.,    Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.-   From the order of the Heteropterida, for example, Cimex spp.,    Triatoma spp., Rhodnius spp., Panstrongylus spp.-   From the order of the Blattarida, for example, Blatta orientalis,    Periplaneta americana, Blattela germanica, Supella spp.-   From the subclass of the Acaria (Acarida) and the order of the Meta-    and Mesostigmata, for example, Argas spp., Ornithodorus spp.,    Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,    Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus    spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,    Sternostoma spp., Varroa spp.-   From the order of the Actinedida (Prostigmata) and Acaridida    (Astigmata), for example, Acarapis spp., Cheyletiella spp.,    Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,    Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,    Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,    Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,    Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are alsosuitable for controlling arthropods which attack agricultural livestocksuch as, for example, cattle, sheep, goats, horses, pigs, donkeys,camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees,other domestic animals such as, for example, dogs, cats, caged birds,aquarium fish and so-called experimental animals such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,cases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey and the like) should be diminished, so that moreeconomical and simpler animal husbandry is possible by the use of theactive compound combinations according to the invention.

The active compound combinations according to the invention are used inthe veterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration such as, for example, by injections (intramuscularly,subcutaneously, intravenously, intraperitoneally and the like),implants, by nasal administration, by dermal administration in the formof, for example, immersing or dipping, spraying, pouring-on,spotting-on, washing, dusting, and with the aid ofactive-compound-comprising moulded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

When used for cattle, poultry, domestic animals and the like, the activecompound combinations can be applied as formulations (for examplepowders, emulsions, flowables) comprising the active compounds in anamount of 1 to 80% by weight, either directly or after 100- to10,000-fold dilution, or they may be used as a chemical dip.

Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

Beetles such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec., Dinoderus minutus.

Dermapterans such as

-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus    augur.

Termites such as

Kalotermes flavicollis, Cryptoternes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristle-tails such as Lepisma saccharina.

Industrial materials in the present context are understood as meaningnon-living materials such as, preferably, polymers, adhesives, glues,paper and board, leather, wood, timber products and paints.

The material which is to be protected from insect attack is veryespecially preferably wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention, or mixtures comprising it, are to beunderstood as meaning, for example:

-   Construction timber, wooden beams, railway sleepers, bridge    components, jetties, vehicles made of wood, boxes, pallets,    containers, telephone poles, wood lagging, windows and doors made of    wood, plywood, chipboard, joinery, or timber products which quite    generally are used in house construction or building joinery.

The active compound combinations can be used as such, in the form ofconcentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellant, if desired desiccants and UV stabilizers, and if desiredcolorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for protecting woodand timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the speciesand the abundance of the insects and on the medium. The optimal quantityto be employed can be determined in each case by test series uponapplication. In general, however, it will suffice to employ 0.0001 to20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

Mineral oils with a boiling range of 170 to 220° C., white spirit with aboiling range of 170 to 220° C., spindle oil with a boiling range of 250to 350° C., petroleum and aromatics with a boiling range of 160 to 280°C., oil of terpentine, and the like are advantageously used.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene are used.

The organic oily or oil-type solvents of low volatility and with anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that the mixture is solubleor emulsifiable in this solvent mixture.

In a preferred embodiment, some of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Aliphatic organochemical solvents which containhydroxyl and/or ester and/or ether groups are preferably used, such as,for example, glycol ethers, esters or the like.

Organochemical binders used for the purposes of the present inventionare the synthetic resins and/or binding drying oils which are known perse and which can be diluted in water and/or dissolved or dispersed oremulsified in the organochemical solvents employed, in particularbinders composed of, or comprising, an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin such as indene/coumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin employed as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances mayalso be used as binders, in amounts of up to 10% by weight. In addition,colorants, pigments, water repellants, odour-masking agents, andinhibitors or anticorrosive agents and the like, all of which are knownper se, can be employed.

In accordance with the invention, the composition or the concentratepreferably comprises, as organochemical binders, at least one alkydresin or modified alkyd resin and/or a drying vegetable oil. Alkydresins which are preferably used in accordance with the invention arethose with an oil content of over 45% by weight, preferably 50 to 68% byweight.

Some or all of the abovementioned binder can be replaced by a fixative(mixture) or plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds, and also crystallizationor precipitation. They preferably replace 0.01 to 30% of the binder(based on 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate,phosphoric esters such as tributyl phosphate, adipic esters such asdi-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amylstearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

Fixatives are based chemically on polyvinyl alkyl ethers such as, forexample, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective timber protection is achieved by industrial-scaleimpregnating processes, for example the vacuum, double-vacuum orpressure processes.

The active compound combinations according to the invention can at thesame time be employed for protecting objects which come into contactwith saltwater or brackish water, such as hulls, screens, nets,buildings, moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

Using the active compound combinations according to the invention,allows the use of heavy metals such as, for example, in bis(trialkyltin)sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I)oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin,tributyltin oxide, molybdenum disulphide, antimony oxide, polymericbutyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltinfluoride, manganese ethylenebisthiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts andcopper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzincethylene-bisthiocarbamate, zinc oxide, copper(I)ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate andtributyltin halides to be dispensed with, or the concentration of thesecompounds substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

-   algicides such as-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentine acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;-   fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;-   molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;-   or conventional antifouling active compounds such as    4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulfone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide    and 2,4,6-trichlorophenylmaleiimide.

The antifouling compositions used comprise the active compoundcombinations according to the invention in a concentration of 0.001 to50% by weight, in particular 0.01 to 20% by weight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, inolluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compound combinations are also suitable for controllinganimal pests, in particular insects, arachnids and mites, which arefound in enclosed spaces such as, for example, dwellings, factory halls,offices, vehicle cabins and the like. They can be employed in domesticinsecticide products for controlling these pests. They are activeagainst sensitive and resistant species and against all developmentalstages.

These pests include:

-   From the order of the Scorpionidea, for example, Buthus occitanus.-   From the order of the Acarina, for example, Argas persicus, Argas    reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus    domesticus, Ornithodorus moubat, Rhipicephalus sanguineus,    Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides    pteronissimus, Dermatophagoides forinae.-   From the order of the Araneae, for example, Aviculariidae,    Araneidae.-   From the order of the Opiliones, for example, Pseudoscorpiones    chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.-   From the order of the Isopoda, for example, Oniscus asellus,    Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus,    Polydesmus spp.-   From the order of the Chilopoda, for example, Geophilus spp.-   From the order of the Zygentoma, for example, Ctenolepisma spp.,    Lepisma saccharina, Lepismodes inquilinus.-   From the order of the Blattaria, for example, Blatta orientalies,    Blattella germanica, Blattella asahinai, Leucophaea maderae,    Panchlora spp., Parcoblatta spp., Periplaneta australasiae,    Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa,    Supella longipalpa.-   From the order of the Saltatoria, for example, Acheta domesticus.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Kalotermes spp.,    Reticulitermes spp.-   From the order of the Psocoptera, for example, Lepinatus spp.,    Liposcelis spp.-   From the order of the Coleptera, for example, Anthrenus spp.,    Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp.,    Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus    oryzae, Sitophilus zeamais, Stegobium paniceum.-   From the order of the Diptera, for example, Aedes aegypti, Aedes    albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora    erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex    pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca    domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp.,    Stomoxys calcitrans, Tipula paludosa.-   From the order of the Lepidoptera, for example, Achroia grisella,    Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea    pellionella, Tineola bisselliella.-   From the order of the Siphonaptera, for example, Ctenocephalides    canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans,    Xenopsylla cheopis.-   From the order of the Hymenoptera, for example, Camponotus    herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,    Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.-   From the order of the Anoplura, for example, Pediculus humanus    capitis, Pediculus humanus corporis, Phthirus pubis.-   From the order of the Heteroptera, for example, Cimex hemipterus,    Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant varieties protectable or notprotectable by plant breeders' rights, such as shoot, leaf, flower androot, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.The plant parts also include harvested material, and vegetative andgenerative propagation material, for example cuttings, tubers, rhizomes,offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seed, also byapplying one or more coats.

The good insecticidal and acaricidal action of the active compoundcombinations according to the invention can be seen from the exampleswhich follow. While the individual active compounds show weaknesses intheir action, the combinations show an action which exceeds a simple sumof actions.

A synergistic effect in insecticides and acaricides is always presentwhen the action of the active compound combinations exceeds the total ofthe actions of the active compounds when applied individually.

The expected action for a given combination of two active compounds canbe calculated as follows, using the formula of S. R. Colby, Weeds 15(1967), 20-22:

If

-   X is the efficacy, expressed as % of the untreated control, when    employing active compound A at an application rate of mg/ha or in a    concentration of m ppm,-   Y is the efficacy, expressed as % of the untreated control, when    employing active compound B at an application rate of m g/ha or in a    concentration of m ppm and-   E is the efficacy, expressed as % of the untreated control, when    employing active compounds A and B at application rates of m and n    g/ha or in a concentration of m and n ppm,    then

$E = {X + Y - \frac{X \cdot Y}{1\text{0}0}}$

If the actual insecticidal kill rate exceeds the calculated value, theaction of the combination is superadditive, i.e. a synergistic effect ispresent. In this case, the actually observed insecticidal kill rate mustexceed the value calculated using the above formula for the expectedinsecticidal kill rate (E).

In this test, for example, the following active compound combinations inaccordance with the present application exhibit a synergisticallyenhanced activity compared to the active compounds applied individually.

USE EXAMPLES

-   Bemisia Test-   Solvent: 7.5 parts by weight of dimethylformamide    Emulsifier: 2.5 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Cotton plants (Gossypium hirsutum) which are infested with eggs, larvaeand pupae of the whitefly Bemisia tabaci are immersed in a preparationof active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed.

TABLE 1 plant-damaging insects Bemisia test Active compound Kill rate in% Active components Concentration in ppm after 10^(d) Ex. (I-b-1) 4 0Pymetrozin 4 0 Ex. (I-b-1) + pymetrozin (1:1) 4 + 4 found* calc.** 90 0*found = activity found **calc. = activity calculated using Colby'sformula

TABLE 2 plant-damaging insects Bemisia test Active compoundConcentration Kill rate in % Active compounds in ppm after 10^(d) Ex.(I-b-1) 20 80 Pyriproxiphen 20 0 Ex. (I-b-1) + pyriproxiphen (1:1) 20 +20 found* calc.** According to the invention 100 80 *found = activityfound **calc. = activity calculated using Colby's formula

1. A composition comprising a mixture of (a) a compound of the formula(I-b-1)

and (b) IKI 220 having the formula

at a ratio of the compound of the formula (I-b-1) to IKI 220 of from10:1 to 1:10.
 2. A method for controlling insect, arachnid, and/or mitepests comprising allowing a mixture according to claim 1 to act on aninsect, arachnid, and/or mite pest and/or a habitat of the pest.
 3. Aprocess for preparing an insecticidal and acaricidal compositioncomprising mixing a mixture according to claim 1 with one or moreextenders and/or surfactants.